Chlormethylation of vat dyes of the pyranthrone, anthanthrone, and dibenzpyrenequinone series



Patented Jan. 19, 1954 UNITED STATES-.. is

MGHLIORMETHYLATION OF VAT DYES OF "THE PYRANTHRONE,

ANTHANTHRONE,

AND DIBENZPYREIQQQUINONE SERIES .Pa Basil "1 h i vestmen t v of polycyclic cum-ones. 1" a lates to the chlormethylationproducts of var, dyes f .the,,.-p @nthmr a; armbandren am :dihenzfemrel-sa le alas o Y@s. u 0.;

throne, 6116.

particularly tl k I chloroinethylder at able new class oi ya colored soluble dyesv V b fiqe, P5 41 tqi aqt ater moniurri and; isothieuroniuni compounds.

conversion, prod" cts may he used ;.to;-dye 5o di tlrfre 'n que iissql iion- Th cl'cnuinones of hlo'rometh' '1 polyqy l area-1S6 valuable as vat dyes themselv jmzlfin the chloroinethyl derivatives are fused in alkali,

the corresponding methyl-compounds are proa is oduc Pyranthrone, for example, gives a leuco ester too insoluble for of the new dyes are quite valuable.

commercial use. However, the-introduction of one or two methylg'roups into the pyranthrone nucleus gives an ester of very good; solubility which prints on cotton in'rich orangebrown hues of excellent fastness properties.

The new chlormethyl polycyclic quinones of alland Tellis A. Martin, Eastqn, Pa, t 'elferal Aniline & Film Corpora- Y., a corporation of Dela-.

g lA ii lict tion December 1, 195 0 e fial No. 198,744

into a large amountof ice anduwater. Theprecipitate; is-collected and ,washedwith; water u until neutral. When it .is desired 'to.-; introduoe;.more

thanltwo ,chlqromethyl igroups,.theidichloro-di- :ingequation: I

methyl.- .ether is reacted. withjzth'e polycyclic; quinone dye in.-.py1ioline'in,thespresence of .alumh num chloride asoatalyst. 3 V

"Thereaction ,may be represented by thefollow- R-lenient 4 f wherein "R represents the pyranthrone,anthana throne, or "diben zpy'renequinone radical and. nis

Thi t -th e iben ien uitbh iwe the pyranthrone, 'anthanthrone, and dibenzpyrenequinone series are produced by dissolving the'pyranthrone, anthanthrone, or dibenzpyrenequinone co'mpoundin-sul'furic acid of at least 95% strength and reacting with a chloralkylating agent such as dichlorodimethyl ether. The

solution wasadd' m thy ce he i' C. iorfoiiir' daysfith'ereaction 'r'n ture poured into ice and water, filtered andthe filter cake washed neutral. Weight 37.1 g. chlorine calc. 9.25% chlorine found7.3 2%. The bulk of the product corresponded,- to a monochloromethylated product which ,on vattin gave golden yellow dyeings of good jastness properties. The shade of the dyeings was somewhat redder than the starting material.

After vatting, thechloromethyl derivative was reduced to the monon'iethyl derivative and could be filtered ofi.

The chloromethyl prqductghas the formula:

anhydrous aluminum chloride. was allowed to raise to 150 C. At 65-70 C., 52 g.

EXAMPLE 2 OHzCl A dimethyl derivative was obtained on vatting which gave orange yellow dyeings of good fastness properties.

EXAMPLE 3 80.0 g. pyridine was added slowly to 320 g, of The temperature of bischloromethyl ether was dropped in slowly. Then at 50-60" C. 33.2 g. of dibenzpyrenequinone was added over a period of one hour. The reaction was poured over 2000 g. of ice and 300 cc. of HCl. The yellow solid which was obtained was washed with dilute HCl and water. Weight, 41.0 g., chlorine calculated 16.3%, found 16.4%.

The analysis indicates that two chloromethyl groups have been introduced. Dyeings on cotton have good fastness properties and aresomewhat redder than the dye of Example 2.

EXAMPLE 4 Eleven grams of anthanthrone were dissolved in 100 cc. of 100% sulfuric acid and 15.0 cc. 0;" bischloromethyl ether. A temperature of 80 C. was held for 48 hours. The new dye was isolated as in Example 1. Weight, 13.0 g.; chlorine calculated 10.0%, found 7.35%.

On vatting, it was reduced to methyl anthanthrone and yielded dyeings of excellent fastness to light and to chlorine. The structure is believed to be the following for the chlormethyl derivative:

EXAMPLE 5 chlorine content of 10.0%. The product has the formula:

CHzCl CHzCl Upon vatting the compound was reduced to the corresponding methyl derivative which gave attractive yellow orange dyeings of excellent fastness properties. The leuco ester of this new dye was made in excellent yield and possessed good solubility unlike the parent dye.

EXAMPLE 6 Chloromethylatio'n of pyranthrone by the aluminum chloride method; preparation of dichloromethylpyranthrone One hundred sixty parts of pyridine are added slowly under mechanical stirring to 640 parts of anhydrous aluminum chloride, allowing the temperature to rise to -160 C. The almost com plete solution was then allowed to cool to 65 C. with stirring and 104 parts of bischloromethyi ether are added fairly rapidly, maintaining the reaction temperature below 70 C. At 55-60 C., 81.2 parts of pyranthrone are added at such rate that the temperature is maintained at 55-60 C. The reaction mixture is heated at 60:2 0. for one hour and then the resulting dark viscous material is poured with hand stirring into a mixture of 2000 parts of ice-water and 600 parts of concentrated hydrochloric acid, chipped ice being added at intervals in such quantities that the temperature does not exceed 30 C. Then precipitated reddish-brown material is collected on a filter, washed well with water and once with ethanol. After drying at 60 C., 112.7 parts of product, which contains 14.8% of chlorine and consists chiefly of dichloromethyl pyranthrone, are obtained, having the same formula as in Example 5.

EXAMPLE 7 When Example 6 was repeated using one-half quantities and extending the reaction time to two hours, a mixture of equal molecular quantities of the dichloromethyland the trichloromethylpyranthrone is obtained (56.5 parts). This material contains 17.1% of chlorine. The formula for the trichloromethyl derivative of pyranthrone 3. The vat dye intermediate di(chloromethyl) dibenzpyrenequinone having the formula:

ClHaC 4. The vat dye intermediate m0no(chloromethyl) anthanthrone having the formula:

CHaGl 5. The vat dye intermediate di(chl0romethy1) pyranthrone having the formula:

6. The vat dye intermediate tri(ehloromethyl) pyranthrone having the formula:

ClHzC OHzCl y DAVID I. RANDALL. TELLIS A. MARTIN.

References Cited in the file of this patent UNITED STATES PATENTS Number Number Name Date Kunz et a1. Aug. 29, 1933 Kunz et a1 Sept. 12, 1933 Koeberle et a1 July 12, 1938 Linch et a1. y Apr. 22, 1941 FOREIGN PATENTS Country Date Great Britain Dec. 7, 1948 Great Britain May 26, 1949 

1. VAT DYES AND VAT DYES INTERMEDIATES OF THE CLASS CONSISTING OF CHLOROMETHYL DERIVATIVES OF PYRANTHRONE, ANTHANTHRONE, AND DIBENZPYRENEQUINONE. 